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Issue 37, 2012
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LnIII2MnIII2 heterobimetallic “butterfly” complexes displaying antiferromagnetic coupling (Ln = Eu, Gd, Tb, Er)

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Abstract

The isostructural heterometallic complexes [LnIII2MnIII2O2(ccnm)6(dcnm)2(H2O)2] (Ln = Eu (1Eu), Gd (1Gd), Tb (1Tb), Er (1Er); ccnm = carbamoylcyanonitrosomethanide; dcnm = dicyanonitrosomethanide) have been synthesised and structurally characterised. The in situ transition metal promoted nucleophilic addition of water to dcnm, forming the derivative ligand ccnm, plays an essential role in cluster formation. The central [LnIII2MnIII2(O)2] moiety has a “butterfly” topology. The coordinated aqua ligands and the NH2 group of the ccnm ligands facilitate the formation of a range of hydrogen bonds with the lattice solvent and neighbouring clusters. Magnetic measurements generally reveal weak intracluster antiferromagnetic coupling, except for the large JMnMn value in 1Gd. There is some evidence for single molecule magnetic (SMM) behaviour in 1Er. Comparisons of the magnetic properties are made with other recently reported butterfly-type {LnIIIxMIII4−x (d-block)} clusters, x = 1, 2; M = Mn, Fe.

Graphical abstract: LnIII2MnIII2 heterobimetallic “butterfly” complexes displaying antiferromagnetic coupling (Ln = Eu, Gd, Tb, Er)

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Publication details

The article was received on 27 May 2012, accepted on 04 Jul 2012 and first published on 04 Jul 2012


Article type: Paper
DOI: 10.1039/C2DT31144E
Citation: Dalton Trans., 2012,41, 11402-11412
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    LnIII2MnIII2 heterobimetallic “butterfly” complexes displaying antiferromagnetic coupling (Ln = Eu, Gd, Tb, Er)

    A. S. R. Chesman, D. R. Turner, K. J. Berry, N. F. Chilton, B. Moubaraki, K. S. Murray, G. B. Deacon and S. R. Batten, Dalton Trans., 2012, 41, 11402
    DOI: 10.1039/C2DT31144E

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